US3926436A

US3926436A - Silver halide element containing polymeric colour forming couplers

Info

Publication number: US3926436A
Application number: US443118A
Authority: US
Inventors: Marcel Jacob Monbaliu; Jan Jozef Priem; Roger Henri Vrydaghs
Original assignee: Individual
Current assignee: Individual
Priority date: 1973-02-26
Filing date: 1974-02-15
Publication date: 1975-12-16
Anticipated expiration: 1992-12-16
Also published as: GB1453057A; DE2407569C2; BE810940A; DE2407569A1

Abstract

Light-sensitive photographic colour elements are described containing polymeric compounds comprising recurring colour coupler or competing coupler units and units derived from a monomer corresponding to the formula:

wherein: R is hydrogen, C1-C4 alkyl or chlorine, X is -O- or -N(R'')- wherein R'' is hydrogen or lower alkyl, Y is a divalent hydrocarbon group which may be interrupted by oxygen and/or sulphur, and M is a cation. The polymeric compounds can be incorporated in hydrophilic colloid coating compositions from latices that do not contain ballasting emulsifying agents, show less foaming tendency, have high compatibility with hydrophilic colloids such as gelatin and make possible to coat thinner layers.

Description

'United States Patent Monbaliu et al.

[ Dec. 16, 1975 22 Filed: Feb. 15, 1974 21 Appl. No.: 443,118

[30] Foreign Application Priority Data Feb. 26, 1973 United Kingdom 9421/73 [52] U.S. Cl. 96/67; 96/74; 96/100;

[51] Int. Cl. G03C 1/40; 603C H72 [58] Field of Search 96/100, 114, 67

[56] References Cited UNITED STATES PATENTS 2,353,262 7/1944 Peterson et al. 96/100 2,976,294 3/1961 Firestine 96/100 3,024,221 3/1962 LeFevre et a1. 260/793 MU 3,356,686 12/1967 Firestine et a1. 96/100 3,370,952 2/1968 Dawson 96/100 3,767,412 10/1973 Monbaliu et al 96/100 Primary Examiner-J. Travis Brown Attorney, Agent, or FirmRobert M. Ashen; Robert J. Schaap [57] ABSTRACT Light-sensitive photographic colour elements are described containing polymeric compounds comprising recurring colour coupler or competing coupler units and units derived from a monomer corresponding to the formula:

wherein:

R is hydrogen, C -C alkyl or chlorine, X is -O or N(R) wherein R is hydrogen or lower alkyl, Y is a divalent hydrocarbon group which may be interrupted by oxygen and/or sulphur, and M is a cation.

The polymeric compounds can be incorporated in hydrophilic colloid. coating compositions from latices that do not contain ballasting emulsifying agents, show less foaming tendency, have high compatibility with hydrophilic colloids such as gelatin and make possible to coat thinner layers.

9 Claims, No Drawings The present invention relates to polymeric colour forming couplers and competing couplers and to photographic silver halide elements containing these polymeric compounds.

It is known that for the production of a photographic colour image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a colour coupler which by reaction with the oxidized developer forms a dye on the areas corresponding to the silver image.

It is also known to improve colour reproduction in photographic colour elements by incorporating therein so-called competing couplers which react with the oxidation products of the developing agent to form colourless compounds. They are used in those instances where such undesirable oxidation products should be rendered ineffective so that degradation of the image quality is inhibited. Colour couplers and competing couplers, when incorporated in photographic light-sensitive silver halide material, should remain immobile and not wander or diffuse through the material from their original site.

Besides colour couplers and competing couplers carrying in their molecule a long chain aliphatic group to prevent diffusion it has also been proposed to use polymeric couplers obtained by addition polymerization of monomeric couplers.

Polymeric couplers are preferably used in the form of latices obtained by emulsion polymerization techniques with the aid of the usual addition polymerization initiators. Interesting emulsion polymerisation techniques are for instance described in Belgian Pat. No. 669,971 according to which latices are formed of polymeric colour couplers by emulsion polymerisation in aqueous gelatin, and in United Kingdom Pat. No. 1,130,581 according to which latices are formed of polymeric couplers by emulsion polymerisation in water.

The incorporation of polymeric couplers in hydrophilic colloid compositions in the form of latices have important advantages over the incorporation of the polymeric or nonpolymeric couplers in the form of solutions in water, water-miscible solvents or waterimmiscible solvents.

Indeed, latices may contain a high percentage of polymer e.g. concentrations up to 50 and nevertheless still possess a relatively low viscosity; when incorporating said latices into emulsions the viscosity of the latter is not influenced. Moreover, by the use of latices there can be dispensed with the use of organic solvents or alkaline solutions as well as with special dispersing techniques for incorporating the coupler compounds.

However, the use of latices also poses a number of difficulties. For example, it is often required to add an extra amount of emulsifying agent when incorporating the latex into the hydrophilic colloid composition e.g. a silver halide emulsion in that the emulsifying agent used in the preparation of the latex does not suffice to stabilize the polymer particles in the hydrophilic colloid. Moreover, the ballast of emulsifying agent may give rise to foaming when dispersing the latex in the hydrophilic colloid and the coated layer often shows repellency spots, streaks and the like coating defects.

It is an object of the present invention to provide latices of polymeric colour couplers and competing couplers that are exempt from the otherwise ballasting emulsifying agents.

It is also an object of the present invention to provide latices of polymeric colour couplers and competing couplers wherein the polymer particles are internally stabilized in the aqueous colloidal dispersion by a polymerically combined emulsifier.

Another object of the present invention is to provide latices of polymeric colour couplers and competing couplers that have reduced foaming tendency and do not give rise to coating defects in hydrophilic colloid coatings.

Still another object of the present invention is to provide latices of polymeric colour couplers and competing couplers which have high compatibility with hydrophilic colloids more particularly gelatin and do not require an external surfactant for being dispersed into the hydrophilic colloid.

A further object is to provide latices of polymeric colour couplers and competing couplers which comprise reduced ballast of emulsifying agent so that it is possible to obtain thinner hydrophilic colloid layers e. g. silver halide emulsion layers which results in increased sharpness.

A still further object is to provide a photographic silver halide colour element comprising in a silver halide emulsion layer or in a hydrophilic colloid layer in water-permeable relationship with a silver halide emulsion layer, a said latex of a polymeric colour coupler or competing coupler.

Other objects and advantages of the invention will become apparent from the description below.

The objects of the present invention have been attained in latices of polymeric compounds that are copolymers comprising recurring units derived from ethylenically unsaturated colour coupler or competing coupler monomers and recurring units derived from monomers corresponding to the formula:

wherein:

R is hydrogen, alkyl, preferably C C, alkyl, or chlorme,

X represents -O- or N(R')-wherein R is hydro gen or lower alkyl e.g. methyl,

Y represents a divalent hydrocarbon group which may be interrupted by oxygen and/or sulphur e.g. alkylene, arylene e.g. phenylene, alkyleneoxyalkylene, alkylenephenylene and alkyleneoxyphenylene, in which the alkylene groups are preferably lower alkylene groups and include straight-chain and branched-chain alkylene, cycloalkylene and substituted alkylene e.g. alkylene substituted by halogen e.g. chlorine and bromine, alkoxy and phenyl, and in which the arylene groups include substituted arylene, and

M represents a cation e.g. hydrogen, a metal atom e.g. sodium and potassium, ammonium and organic amine, e.g. diethanolamine, triethylamine.

Representative monomeric compounds corresponding to the above general formula I can be found in British Pat. No. 1,009,186 and US. Pat. No. 3,024,221. Particularly suitable results are obtained with mono- 3 mers in which Y stands for a straight-chain or branched-chain C C alkylene group i.e. with sulphoethyl, sulphopropyl and sulphobutyl esters of acrylic acid and a-substituted acrylic acids and to a less degree with the N-sulphoethyl, N-sulphopropyl and N-sulphobutyl acrylamides or a-substituted acrylamides.

The present invention thus provides latices of polymeric compounds that are copolymers comprising recurring units derived from ethylanically unsaturated colour coupler or competing coupler monomers and recurring units derived from monomers corresponding to the above formula.

The present invention further provides a photographic silver halide colour element comprising a support and at least one silver halide emulsion layer wherein the said silver halide emulsion layer and/or a hydrophilic colloid layer in water-permeable relationship therewith comprises a polymeric latex the polymer of which being a copolymer as defined above.

As is known in the art the polymeric couplers may also comprise units of copolymerized ethylenically unsaturated monomers that are not capable of oxidative coupling with aromatic primary amino compounds for example acrylic acid, a-chloroacrylic acid, a-alkacrylic acids, wherein the substituting alkyl contains from 1 to 4 carbon atoms e.g. methyl, ethyl and n-propyl, the esters and amides derived from acrylic acid, a-chloroacrylic acid and these a-alkacrylic acids, such as acrylamide, methacrylamide, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate, vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate, acrylonitrile, methacrylonitrile, aromatic vinyl compounds such as styrene and its derivatives, e.g. vinyl toluene, vinyl acetophenone and sulphostyrene, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers such as vinyl ethyl ether, maleic acid esters, N-vinyl-2-pyrrolidone, N- vinylpyridine, 2- and 4-vinyl-pyridine.

As is known in the art, the ethylenically unsaturated monomers suitable for being copolymerized with the monomeric colour couplers or competing couplers and the monomeric sulphoesters or sulphoamides described above can be chosen so that the physical and/or chemical properties of the resulting copolymer such as its solubility, its flexibility, its thermal stability, etc., are favourably influenced. For example, it is known that methacrylic acid and styrene when used together as comonomers e.g. in a ratio of about to about 30 and about 50 to about 30 percent by weight respectively relative to the total amount of monomers give particularly good results in polymeric colour couplers in that they yield dye images of improved sensitometric properties and improved stability against moisture and heatv Other favourable comonomers are acrylic acids and acrylates either used alone or in combination.

The monomeric ethylenically unsaturated colour couplers or competing couplers for being copolymerised in accordance with the present invention are generally of the type respresented by the formula II II R wherein:

R is hydrogen, alkyl, preferably C -C alkyl, or chlorine 4 Q is a colour coupler or competing coupler residue capable of coupling with an oxidized aromatic primary amine colour developing agent.

Colour couplers and competing couplers are well known in the art of silver halide colour photography. The monomers represented by the above formula II comprise a residue Q of well known coupler compounds for example 1, a residue of a cyan-forming colour coupler of the phenol or naphthol type e.g. of the formula:

wherein A is a single chemical bond or a bivalent organic group linking the ethylenically unsaturated group of the formula II to the colour coupler residue,

R represents hydrogen, a substituent of the type well known in phenol or naphthol colour couplers such as halogen alkyl or aryl, or the atoms necessary to complete a fused-on benzene nucleus which may be substituted, and

Y represents a hydrogen atom in the case of 4- equivalent couplers or a substituent which splits off upon colour development thus conferring to the colour coupler a 2-equivalent character e. g. a halogen atom such as chlorine, an acyloxy group, an alkoxy, aryloxy, or heterocycloxy group, an alkylthio, arylthio or heterocyclic thio group such as tetrazolylthio group, or phenylazo group etc.

2. a residue of a magenta-forming colour coupler of the pyrazolone or indazolone type e.g. of the formula:

wherein:

R is substituent of the type well-known in the l-position of 2-pyrazolin5-one colour couplers e.g. alkyl including substituted alkyl e.g. haloalkyl such as fluoroalkyl, cyanoalkyl and benzyl, or aryl including substituted aryl e.g. phenyl which may be substituted by alkyl, halogen, alkoxy, haloalkoxy, alkyl sulphonyl, haloalkyl sulphonyl, alkylthio, haloalkylthio, etc., and

Y is hydrogen in the case of 4-equivalent couplers or a substituent which splits off upon colour development thus conferring to the colour coupler a 2-equivalent character e.g. a halogen atom such as chlorine, an acyloxy group, an alkoxy group, an aryloxy group or a heterocycloxy group, an alkylthio group, an arylthio group or a heterocyclic thio group such as tetrazolylthio, a phenylazo group, etc.

3. a residue of a yellow forming colour coupler of the acylacetamide type, especially the acylacetanilide type for example an anilino carbonylacetophenyl group or a benzoylacetamidophenyl group wherein both aryl group may be substitutedby substituents well known in yellow-forming colour couplers e.g. alkyl, alkoxy, halogen, alkylthio, alkylsulphonyl, etc. and wherein the active methylene group may carry a substituent conferring to the colour coupler a 2-equivalent character e.g. a halogen atom such as chlorine, acyloxy, an alkoxy, aryloxy or heterocycloxy group, an alkylthio, arylthio or heterocyclic thio group, etc.

4. a competing coupler residue e.g. of the type described for the above colour couplers wherein one hydrogen atom of the active methylene group is replaced by alkyl, preferably C -C alkyl including substituted alkyl e.g. benzyl, preferably a competing coupler residue of the 2-pyrazolin-5-one type.

Examples of monomeric colour couplers suitable for copolymerization in accordance with the present invention can be found in the literature e.g. in Belgian Pat. Nos. 584,494 602,516 and 669,971, in British Pat. Nos. 967,503 1,130,581 1,247,688 and 1,269,355, in U.S. Pat. No. 3,356,686 and in British Pat. Application No. 59792/70.

Representative examples are:

Z-methylsulphonylamino-S-methacrylaminophenol 2-methylsulphonylamino-4-chloro-5-methacrylaminophenol 2-phenylsulphonylamino-5-methacrylaminophenol 2-(4-chlorophenyl) sulphonylamino-S-methacrylaminophenol 2-(4-sec.butylphenyl) crylaminophenol 2-ethoxycarbonylamino-S-methacrylaminophenol 2-n-butylureido-5-methacrylaminophenol 2-benzoylamino-5-methacrylaminophenol 2-o-methylbenzoylamino-S-methacrylaminophenol 2-acetylamino-5-methacrylaminophenol Z-p-methoxybenzoylamino-S-methacrylaminophenol 2-o-chlorobenzoxylamino-5-methacrylaminophenol 2-p-t.butylbenzoylamino-S-methacrylaminophenol 1 -hydroxy-N-B-acrylamidoethyl-2-naphthamide 1-hydroxy-N-B-vinyloxyethy1-2-naphthamide 1-hydroxy-4-chlor0-N-B-methacrylamidoethyl-2- naphthamide 1 1-hydroxy-4-chloro-N-,B-acrylamidoethyl-2-naphthamide 2-methacrylamido-4,6-dichloro-5-methylphenol 1-benzyl-3-acrylamido-2-pyrazolin-5-one l-( 2-cyanoethyl )-3-meth acrylamido-2-pyrazolin- 5-one 1-( 3 ,4-dichlorobenzyl )-3 -methacrylamido-2-pyrazolin-5-one 1-(2,2,2-trifluoroethyl)-3-methacrylamido-2-pyrazo lin-S-one 1-p-( l ,1 ,2-trifluoro-2-chloroethoxy)phenyl-3-methacrylamido-2-pyrazolin-5-one 1-phenyl-3-methacrylamido-2-pyrazolin-5-one l-o-bromophenyl-3-methacrylamido-Z-pyrazolin- 5-one l-( 2 ,4 ,6 -trichlorophenyl )-3-acrylamido-2-pyrazolin-5-one p-methacrylamidobenzoylacetanilide sulphonylamino-S-metha- 6 N-[ 3-methoxy-4-(o-methoxybenzoylacetylamino methacrylamide p-methacrylamido-benzoylacetaniside 2-chloro-4-methacrylamido-benzoylacetanilide l-phenyl-3-methacrylamido-4-methyl-2-pyrazolin- 5-one 1-p-methylsulphonylphenyl-3-methac rylamido-4- methyl-2-pyrazolin-5-one 1-( 2-chloro-4-methylsulphonylphenyl )-3-methacrylamido-4-methyl-Z-pyrazolin-S-one 1-( 2,4,6-trichlorophenyl)- ltrichlorophenyl )-3- methacrylamido-4-methyl-2-pyrazolin-5-one l-m-chlorophenyl-3-methacrylamido-4-methyl-2- pyrazolin-S-on The latices of the polymeric colour forming couplers or competing couplers can be prepared by emulsion polymerization as described in Belgian Pat. No. 669,971 and UK. Pat. No. 1,130,581 referred to above.

Examples of polymerization initiators and suitable solvents as well as instructions relating to the formation of the initial emulsions and/or suspensions are set forth in these Patents. 7

Amongst the polymerization initiators suitable for use in the above emulsion polymerization process may be mentioned: persulphates such as ammonium and potassium persulphate, azonitrile compounds such as 4,4-azo-bis(4-cyanovaleric acid) as well as peroxide compounds such as benzoyl peroxide, hydrogen peroxide.

The aqueous dispersion of the polymerisable composition may optionally contain conventional emulsifiers although they can be omitted and, if used, can usually be employed in smaller proportion than is possible with known procedures where no comonomeric emulsifier is used.

The comonomeric sulphoesters and sulphoamides of acrylic acids and a-substituted acrylic acids are generally used in amounts ranging from about 0.5 to about 15, preferably from about 1 to about 10% by weight relative to the weight of other polymerisable ethylenically unsaturated monomers.

The latices obtained generally comprise between about 2 and about 50 by weight of polymeric colour coupler or competing coupler in respect of the total amount of latex.

The polymeric couplers according to the present invention can be. characterized by their so-called equivalent molecular weight. By equivalent molecular weight is understood the number of grams of polymer containing 1 mole of polymerized monomeric coupler. It can be compared with the molecular weight of the non-polymeric classical non-migratory couplers. The equivalent molecular weight of the polymeric couplers according to the invention can vary within very wide limits, preferably from about 200 to about 2000.

The following preparations illustrate how the latices of the polymeric colour couplers and competing couplers of the present invention can be prepared.

PREPARATION 1 Latex of the copolymer of l-phenyl-3-methacrylamido-4-methyl-2-pyrazolin-5-one, butylacrylate and the sodium salt of 2-sulphoethyl methacrylate.

A suspension of 260 ml of demineralized water, 52.5 g of 1-phenyl-3-methacrylamido-4-methyl-2-pyrazolin- 5-one and 37.5 ml of a 10 aqueous solution of the sodium salt of 2-sulphoethylmethacrylate was stirred for 30 min. while introducing nitrogen. The suspension was heated to 90C whereupon 6.75 g of n-butylacrylate and 8.5 ml ofa 1 aqueous solution of the sodium salt of 4.4-azo-bis(4-cyanovaleric acid) were added. The temperature was raised to the reflux temperature and over a period of 30 min. were added 12 g of n-butylacrylate and 29 ml of a 1 aqueous solution of the above polymerization initiator. The mixture was refluxed for 1 hour and the latex obtained was cooled and filtered.

Yield 260 ml of very stable latex.

Concentration of solids per 100 ml of latex 24.2 g

Concentration of polymer per 100 ml of latex: 24.0 g

Equivalent molecular weight 342 PREPARATION 2 Latex of the copolymer of l-p-methylsulphonylphenyl-3-methacrylamido-4-methyl-2-pyrazolin-5-one, butylacrylate and the sodium salt of 2-sulphoethyl methacrylate.

A suspension of 170 ml of demineralized water 40 g of l-p-methylsulphonylphenyl-3-methacrylamido-4- methyl-2-pyrazolin-5-one, 2.5 g of the sodium salt of 2-sulphoethylmethacrylate and 7.5 g of butylacrylate was heated to 90C whereupon 15 ml of a 1 aqueous solution of the sodium salt of 4,4'-azo-bis(4-cyanovaleric acid) were added. The temperature was raised to the reflux temperature. The mixture was refluxed for 1 hour and the latex obtained was cooled and filtered.

Yield 250 ml of very stable latex.

Concentration of solids per 100 ml of latex 15.3

Concentration of polymer per 100 ml of latex: 15.2

Equivalent molecular weight 452 PREPARATION 3 Latex of the copolymer of 1-phenyl-3-rnethacrylamido-Z-pyrazolin-5-one. butylacrylate and the sodium salt of 2-sulphoethyl methacrylate.

a. A suspension of 700 ml of demineralized water,

160 g of l-phenyl-3-methacrylamido-2-pyrazolin- 5-one and g of the sodium salt of 2-sulphoethyl methacrylate was stirred for 30 min. while introducing nitrogen and heated to 50C. After addition of 10 g of butylacrylate the mixture was heated to 90C and 25 ml of a l aqueous solution of the sodium salt of 4,4-a2o-bis(4-cyanovaleric acid) were added.

The temperature rose to 95C and after 5 min.. g of butylacrylate and 75 ml of the above solution of polymerization initiator were added dropwise in 30 min. The mixture was further stirred for 30 min. and then cooled and filtered.

Yield 800 m1 of very stable latex.

Concentration of solids per 100 ml of latex 20.75 g

Concentration of polymer per 100 ml of latex 20.6 g

Equivalent molecular weight 288 b. Another latex was prepared in a similar way from 120 g of l-phenyl-3-methacrylamido-2-pyrazolin- 5-one. 70 g of butyl acrylate and 5 g of the sodium salt of 2-sulphoethyl methacrylate.

Yield 800 ml of very stable latex.

Concentration of solids per 100 ml of latex 20.6 g

Concentration of polymer per 100 ml of latex: 20.5 g

Equivalent molecular weight 409 0. Another latex was prepared in a similar way from 96 g of l-phenyl-3-methacrylamido-2-pyrazolin- 8 5-one. 132 g of butylacrylate and 12 g of the sodium salt of 2-sulphoethyl methacrylate. Yield 800 ml of very stable latex. Concentration of solids per 100 ml of latex 20.5 g Concentration of polymer per 100 ml of latex 20.35

Equivalent molecular weight 640 PREPARATION 4 Latex of the copolymer of l-benzyl-3-methacrylamido-Z-pyrazolin-S-one, styrene and the sodium salt of 2-sulphoethyl methacrylate.

A mixture of 175 ml of demineralized water, 20 g of l-benzyl-3-methacrylamido-2-pyrazolin-5-one, 10 g of styrene and 2.5 g of the sodium salt of 2-sulphoethyl methacrylate was heated to 90C while introducing nitrogen.

After addition of 8 ml of a 1 aqueous solution of the sodium salt of 4,4-azo-bis-(4-cyanovaleric acid) the mixture was left standing for 10 min. whereupon 17.5 g of styrene and another 17 ml of the said 1 71 aqueous solution were added dropwise while keeping the mixture at the reflux temperature. Refluxing was continued for min. and then the latex formed was cooled and filtered.

Yield 210 ml of very stable latex.

Concentration of solids per 100 ml of latex 14.00 g

Concentration of polymer per 100 ml of latex 13.9

Equivalent molecular weight 867.

PREPARATION 5 Latex of the copolymer of p-methacrylamidobenzoyl acetaniside, butyl acrylate, methacrylic acid and the sodium salt of 2 sulphoethyl methacrylate.

Nitrogen was introduced into a suspension of 300 ml of demineralized water, 40 g of p-methacrylamidobenzoyl acetaniside (mp 168C) prepared from p-aminobenzoyl acetaniside and methacryloyl chloride, and 50 ml of a 10 aqueous solution of the sodium salt of 2-sulphoethyl methacrylate. The mixture was heated to C whereupon 12 g of methacrylic acid and 7 g of butyl acrylate were added. The temperature was raised to C and 25 ml of a l aqueous solution of the sodium salt of 4,4'-azo-bis(4cyanovaleric acid) were added.

After 10 min., a mixture of 23 g of methacrylic acid and 13 g of butylacrylate was added dropwise in 30 min. with refluxing. After 30 min. the latex formed was cooled and centrifuged.

Yield 390 ml of very stable latex.

Concentration of solids per ml of latex Concentration of polymer per 100 ml of latex Equivalent molecular weight 995.

PREPARATION 6 30 min. Refluxing was continued for 30 min. and the latex obtained was cooled and centrifuged.

Yield 400 ml of very stable latex.

Concentration of solids per 100 ml of latex 19.5 g

Concentration of polymer per 100 ml of latex 19.4 g

Equivalent molecular weight 600 PREPARATION 7 Latex of the copolymer of 2-methylsulphonylamino- 5-acrylamidophenol, butylacrylate and the sodium salt of 2-sulphoethyl methacrylate. This latex was prepared in the same way as the latex of preparation 6 from 20 g of 2-methyl sulphonylamino-S-acrylamidophenol, 27.5 g of butyl acrylate and 2.5 g of the sodium salt of 2-sulphoethyl methacrylate.

Yield 250 ml of very stable latex Concentration of solids per 100 ml of latex: 15.10 g

Concentration of polymer per 100 ml of latex: 15.00

Equivalent molecular weight 707 PREPARATION 8 Latex of the copolymer of 1-hydroxy-4-chloro-N-B- acrylamidoethyl-2-naphthamide, butylacrylate and the sodium salt of 2-sulphoethylmethacrylate.

Nitrogen was introduced for 30 min. into a suspension of 350 ml of demineralized water, 50 g of lhydroxy-4-chloro-N-B-acrylamidoethyl-Z-naphthamide and 5 g of the sodium salt of 2-sulphoethyl methacrylate. The mixture was heated to 70C and 15 g of butyl acrylate were added. The mixture was further heated to 90C and 15 ml of a l aqueous solution of the sodium salt of 4,4-azo-bis(4-cyanovaleric acid) were added. The mixture was refluxed for 10 min. whereupon 30 g of butyl acrylate and 35 ml of the above 1 aqueous solution were added. After 30 min., the latex was cooled and filtered.

Yield 400 ml of very stable latex Concentration of solids per 100 ml of latex 15.6 g

Concentration of polymer per 100 ml of latex 15.5

Equivalent molecular weight 851 PREPARATION 9 Latex of the copolymer of l-phenyl-3-methacrylamido-2-pyrazolin-5-one, butylacrylate and the sodium salt of p-sulphophenyl methacrylate.

A suspension of 350 ml of distilled water, 40 g of l-phenyl-3-methacrylamido-2-pyrazolin-5-one, and 5 g of the sodium salt of p-sulphophenyl methacrylate was rinsed with nitrogen for 30 min. and then heated to 90C. Then, 25 g of butyl acrylate and 25 ml of a l aqueous solution of the sodium salt of 4,4'-azobis(4- cyanovaleric acid) were added. The mixture was refluxed for 5 min. and 30 g of butyl acrylate and 25 ml of the said 1 aqueous solution were added in 30 min. Refluxing was continued for 30 min. whereupon the latex was filtered.

Yield 360 ml.

Concentration of solids per 100 ml of latex 10.9 g

Concentration of polymer per 100 ml of latex: 10.7 g

Equivalent molecular weight 1 130.

PREPARATION l0 Latex of the copolymer of 1-phenyl-3-methacrylamido-2-pyrazolin-5-one, butyl acrylate and the sodium salt of N-2-sulphoethyl methacrylamide.

Nitrogen was introduced into a suspension of 175 ml of water, 30 g of l-phenyl-3-methacrylamido-2-pyrazolin-S-one, 5 g of butylacrylate and 2.5 g of the sodium salt of N-2-sulphoethyl methacrylamide. The mixture was heated to C and 5 ml of a 1 aqueous solution of the sodium salt of 4,4-azo-bis(4-cyanovaleric acid) were added. The temperature was raised to the reflux temperature and in 30 min., 12.5 g of butyl acrylate and 20 ml of the initiator solution were added. Refluxing was continued for 30 min. whereupon the latex was partly concentrated by evaporation, cooled and filtered.

Yield 170 ml of latex.

Concentration of solids per ml of latex 15.9 g

Concentration of polymers per 100 ml oflatex: 15.8 g

Equivalent molecular weight 446.

The latices according to the present invention are used in photographic colour elements either in a silver halide emulsion layer or a hydrophilic colloid layer in water-permeable relationship with the said emulsion layer. The latices of polymeric colour couplers are preferably incorporated in a silver halide emulsion layer whereas the latices of polymeric competing couplers are preferably incorporated in one or more intermediate hydrophilic colloid layers in water-permeable relationship with the emulsion layers.

In dispersing the latices according to the invention into the hydrophilic colloid composition e.g. an aque ous gelatin solution or a gelatino silver halide emulsion there can be dispensed with the use of an external ballasting emulsifying agent or reduced amounts of emulsifying agents can be used so that it is possible to reduce the thickness of the coated layers which results in increased sharpness. The latices according to the invention also produce less foam when incorporated into the hydrophilic colloid coating composition.

For example, when the latices of preparations 3a, 4, 5, 6 and 8 hereinbefore were admixed with a conventional photographic silver halide colour emulsion no supplemental amount of emulsifier was necessary to stabilize the latex polymer in the emulsion. As shown in the following table, the latices corresponding to those of preparations 3a, 4,5,6, and 8 but prepared in the conventional way, i.e. in the presence of 5 g of sodium oleyl methyl tauride (OMT) per 100 g of monomers used instead of the sodium salt of 2-sulphoethyl methacrylate, required a supplemental amount of OMT to be stabilised in the emulsion.

These conventional polymeric coupler latices also produced more foam as is illustrated in the following table. The volume foaming was measured according to the Ross-Miles method (ASTM D 1173/53) after 0 and 5 min.

In the following table, the conventional latices corresponding to those of preparations 3a, 4,5,6 and 8 are designated A to E respectively.

. Table-continued Latex Amount of emulsivolume fier ballast in foaming g per I g polymer 0 min. min.

E l0 l6 14 The polymeric couplers of the present invention may be used in various kinds of photographic colour materials which include negative, positive as well as reversal material. Photographic multilayer colour materials usually comprise at least one blue-sensitive silver halide emulsion layer with colour coupler for yellow, at least one green-sensitized silver halide emulsion layer with colour coupler for magenta and at least one red-sensitized silver halide emulsion layer with colour coupler for cyan. These colour materials may further comprise one or more intermediates layers, filter layers and protective surface layers.

The hydrophilic colloid used as the vehicle for the silver halide emulsion layer and the other hydrophilic colloid layers may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N- vinyl pyrr'olidone, etc., gelatin being preferred. If desired compatible mixtures of two or more of these colloids may be employed.

The silver halide emulsion layer may comprise various silver halides as the sensitive halide such as silver bromide, silver chloride, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.

The photographic colour elements comprising the polymeric couplers of the present invention may comprise as supports paper, glass, cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials.

In the development of the exposed photographic colour materials aromatic primary amino developing agents are used forming dyestuffs with the polymeric colour couplers of the present invention and colourless compounds with the polymeric competing couplers of the present invention. Suitable developing agents are p-phenylene diamine and derivatives e.g. N,N-diethylp-phenylene diamine, N-butylN-sulphobutyl-p-phenylene diamine, 2-amino-S-diethyIamino-toluene, 4- amino-N-ethyl-N( B-methane sulphonamidoethyl )-mtoluidine, N-hydroxyethyl-N-ethyl-p-phenylene diamiie etc.

The following examples illustrate the present invention.

EXAMPLE 1 a. Comparison material A 109 g of a silver bromoiodide emulsion (2.3 mole of iodide) which comprises per kg an amount of silver halide equivalent to 47 g of silver nitrate and 73.4 g of gelatin, are diluted with 185 g of a 7.5 aqueous solution of gelatin and 100 g of distilled water. To the emulsion obtained are added with stirring 23 ml of the latex prepared according to preparation 6 of British Pat. application No. 59792/60 which corresponds to 0.006 mole of polymerised monomeric colour coupler. After the addition of the common additives such as stabilizers, wetting agents and hardeners the necessary amount of distilled water is added to obtain 575 g.

The emulsion obtained is coated on a cellulose triacetate support pro rata of 125 g per sq.m. The emulsion 12 layer is dried and overcoated with a gelatin antistress layer. b. Material B 2-amino-5-diethylaminotoluene hydrochloride Calgon anhydrous sodium sulphite anhydrous sodium carbonate potassium bromide water to make litre (pH: I065) The developed materials were treated for 5 min. at 24C in an acid hardening fixer of the following composition:

water 800 ml anhydrous sodium thiosulphate 200 g sodium bisulphite 12 g glacial acetic acid 12 ml borax l0 aq. 20 g potassium alum 15 g water to make I000 ml (pH:4.l0)

The materials were rinsed for 10 min. with water and treated in a bleach bath of the following composition:

anhydrous potassium bromide 20 g potassium alum 5 g potassium dichromate 5 g water to make I litre (pH:3.l

After bleaching, the materials were rinsed with water for 5 min. and treated for 5 min. at 24C in the above acid hardening fixer.

After a final rinsing for 10 min. the materials were dried.

Cyan coloured wedge images were obtained and the sensitometric results are listed in the table.

Table material relative speed gamma D A l 00 l .25 2 .04 B l 32 l .93 3.70

The above results show that the latex of the invention provides higher speed, gamma and maximum density.

EXAMPLE 2 l 17 g of a silver bromoiodide emulsion (2.3 mole of iodide) which comprises per kg an amount of silver halide equivalent to 47 g of silver nitrate and 73.4 g of gelatin, are diluted with 192.5 g of a 7.5 aqueous solution of gelatin and g of distilled water. To the emulsion obtained are added with stirring 12 ml of the latex. prepared according to preparation 3b which corresponds to 0.006 mole of polymerised monomeric colour coupler. After the addition of the common additives such as stabilizers, wetting agents and hardeners the necessary amount of distilled water is added to obtain 720 g.

The emulsion obtained is coated on a cellulose triacetate support pro rata of l25 g per sq.m. The emulsion layer is dried and overcoated with a: gelatin antistress layer. g

After drying the material formed is exposed for 1/20 sec. through a continuous wedge with constant 0.30 and then processed as described in example 1.

A magenta wedge image was obtained.

EXAMPLE 3 A material was prepared as described in example 1 with the difference that now 48 ml of the latex prepared according to preparation 5, which corresponds to 0.006 mole of polymerised monomeric colour coupler were added.

After drying the material formed was exposed to 1/20 sec. through a continuous wedge with constant 0.30 and then developed for 8 min. at 20C in a developing bath of the following composition:

N.N-diethyl-p-phenylene diamine sulphate hydroxylamine sulphate sodium hexametaphosphate anhydrous sodium sulphite anhydrous potassium carbonate potassium bromide water to make The developed material was treated for 2 min. at l820C in an intermediate bath comprising 30 g of sodium sulphate in 1 liter of water.

The material was rinsed for 15 min. with water and treated in a bleach bath of the following composition:

borax 20 g potassium bromide l5 g anhydrous potassium bisulphate 4.2 g potassium hexacyanoferrate(lll) g water to make I litre After bleaching, the material was rinsed with water for min. and fixed in an aqueous solution of 200 g of sodium thiosulphate per liter.

After a final rinsing for min. the material was dried.

A yellow coloured wedge image was obtained.

EXAMPLE 4 A photographic multilayer negative material A was composed as follows:

1. a common film support,

2. two red-sensitized silver halide emulsion layers each containing a colour coupler for cyan and a mask-forming compound, the undermost emulsion layer being of lower speed than the uppermost emulsion layer,

3. an intermediate gelatin layer,

4. two green-sensitized silver halide emulsion layers each containing a colour coupler for magenta and a mask-forming compound, the undermost emulsion layer being of lower speed than the uppermost emulsion layer,

5. a yellow gelatin filter layer,

6. two non-spectrally sensitized blue-sensitive silver halide emulsion layers each containing a yellowforming colour coupler, the uppermost emulsion V14 layer having higher speed than the undermost emulsionlayer, and

7. a protective gelatin coating For comparison purposes a material Bwas prepared in exactly the same way as material A with the only difference that both the gelatin-intermediate layer and the filter layer comprise per sq.m ,3 ml of the latex of the polymericcompeting coupler according to preparation 2, which corresponds to l millimole of polymerized monomeric coupler.

Samples of both materials were exposed to a wedge through a blue, green and red filter and subjected to common negative colour processing for the formation of the yellow, magenta and cyan separation images. The developing agent used was 2-amino-5-[N-ethyl- N(B-methylsulphonylamino)ethyl]amino toluene sulphate.

The separation images of material B showed purer colours than those of material A.

We claim:

1. A photographic colour element comprising a support and at least one light-sensitive silver halide emulsion layer wherein the element comprises a copolymer latex containing recurring units derived from a first ethylenically unsaturated monomer which will undergo oxidative coupling with an aromatic primary amino compound corresponding to the formula:

wherein:

R is hydrogen, C C., alkyl or chlorine, and Q is a moiety which will undergo oxidative coupling with an aromatic primary amino compound, and recurring units derived from a second monomer corresponding to the formula:

wherein:

R is hydrogen, C -C alkyl or chlorine,

X is O or N(R) wherein R is hydrogen or lower alkyl,

Y is a divalent hydrocarbon group which may be interrupted by oxygen and/or sulphur, and

M is a cation.

2. A photographic element according to claim 1, wherein in the said formula Y represents a straightchain or branchedchain C -C alkylene group.

3. A photographic element according to claim 2, wherein in the said formula X is -O.

4. A photographic element according to claim 1, wherein in the said formula Q is a moiety of a phenol, naphthol, pyrazolone, indazolon or acylacetamide coupler.

5. A photographic element according to claim 1, wherein the polymer comprises recurring units of additional ethylenically unsaturated monomers which are not capable of oxidative coupling with aromatic primary amino compounds.

6. A photographic element according to claim 5, wherein the said additional monomers are one or more members selected from the group consisting of acrylic 16 colour coupler and is present in a light-sensitive silver halide emulsion layer.

9. A photographic element according to claim 1, wherein the said polymeric compound is a polymeric competing coupler and is present in an intermediate non-light-sensitive water-permeable colloid layer of the photographic element.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. I 3, 926, 4:36

DATED December 16, 1975 INVENTOR(S) I Marcel Jacob MONBALIU ET AL It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:

Title Page, in the heading, the Assignee should read Agfa -Gevaert,

N.Va lVIortsel, Belgium Title Page, in the heading, "Attorney, Agent, or Firm Robert M.

Ashen; Robert J. Schaap" should read A. W. Breiner Column 5, line 7, "group" should read groups Column 6, line 11 should read l-(2,4, 6-trichloropheny1)-3- Column 7, line 4, after "added" insert Column 14, claim 2, line 52, "branchedchain" should read branchedchain Signed and Scaled this Twenty-eighth Day of June 1977 [SEAL] Arrest:

O RUTH c. MASON c. MARSHALL DANN Ar esting Office Commissioner oj'larenrs and Trademarks E

Claims

2. A photographic element according to claim 1, wherein in the said formula Y represents a straight-chain or branchedchain C2-C4 alkylene group.

3. A photographic element according to claim 2, wherein in the said formula X is -O-.

6. A photographic element according to claim 5, wherein the said additional monomers are one or more members selected from the group consisting of acrylic acid, methacrylic acid, esters and amides derived from these acids and styrene and its derivatives.

7. A photographic element according to claim 1, wherein the polymeric compound is incorporated into the coating composition of the said emulsion layer or hydrophilic colloid layer from an aqueous dispersion (latex).

8. A photographic element according to claim 1, wherein the said polymeric compound is a polymeric colour coupler and is present in a light-sensitive silver halide emulsion layer.